Treatment of hydrocarbon oils



March 13, 1934.

G. EGLOFF 1,950,721

TREATMENT OF HYDROCRBON OILS Filed Feb. l0. 1930 www Fatenteol ii/lar.,` i3, @354i TT liiiimll TREATMENT @F RGCARBON @MLS Gustav lEglod, Chicago, lill., assigner to lllniversall @il Products Qompany, Chicago, lill., a corporation ci South Dakota Application February it, i930, Serial No. 127,126 2 El. (lill. itt-d2) This invention relates to a process for the treatment of hydrocarbon oils and refers more particularly to a process for thehydrogenation of oils at elevated temperatures.

Among the objects of the process is to increase the yield ci the lower boiling products made by the thermal decomposition or cracking of higher boiling oils; to saturate in part the more highly unsaturated hydrocarbons, especially those which form gums, polymers and other undesirable materials in the motor fuel product; and to desulphurize in part the hydrocarbons to render them more suitable for motor fuel and to facilitate and reduce the cost oi refining.

It is not the purpose oi this invention necessarily to completely saturate the hydrocarbons of the olefin series to produce paramn hydrocarbons, but rather to add hydrogen in regulated amounts to the more highly unsaturated hydrocarbons for the aforementioned purposes. In the present invention, the hydrocarbons are treated in the vapor state. Gasoline, which is the major product of the cracking process, contains highly unsaturated hydrocarbons which upon standing polymerize and oxidize to form gums, tars, and other undesirable substances. The presence of sulphur compounds in a motor fuel may result in destructive corrosion oi the crank case and other parts of the motor during combustion and may also result in the destructive corrosion of the cracking or distillation equipment.

Among the objects of my invention is the minimizing of these objectionable features.

In the specific embodiment otmy invention, the

oil in a vapor state is mixed with a metallic hydride or mixture of hydrides made by heating metals oi the alkali or alkaline earth series such as sodium, potassium, calcium, barium, strontium, magnesium, etc., with hydrogen. The mixture of oil and hydride is subjected to treatmentwith steam at an elevated temperature, the hydride reacts with the steam forming hydrogen and the corresponding oxides of metals which may have a catalytic eect in the reaction including the hydrogenation, desulphurization and the conversion or cracking.

In the operation of the process of my invention, the hydrides preferably in a iinely divided state are introduced simultaneously with steam in those portions of the cracking system where the oil is in the vapor statee g., in the reaction chamber and dephlegmator and vapor lines or enlarged portion thereof. The steam reacts with the nnely divided hydrides forming hydrogen in situ. The newly liberated hydrogen, which is more active than ordinary molecular'hydrogen and is someran times spoken of as being in the nascent state, reacts with the chemically unsaturated portions of the oil vapors as well as with sulphur compounds, saturating in part the olefinic hydrocarbons and reducing some of the sulphur compounds to hydrogen sulphide which may readily bc re moved from the iinal products.

As further examples ci hydrides, I may use those of sodium, potassium, calcium, magnesium, zinc, aluminum, iron, tin and others, including alloys and amalgams preferably the metals which are electro-positive to hydrogen and which liberate vhydrogen from steam. The corresponding oxides of the metals formed by the reaction with steam have some catalytic reaction in promoting .the hydrogenation and desulphurization reaction as well as assisting in the cracking reaction. The use of finely divided hydrides has an additional advantage in that the finer the hydride the greater the surface exposure and consequently the greater the velocity or rate of reaction. In addition to the above I may also add molecular hydrogen to the materials undergoing reaction in order to assist in the reaction, or I may add gases containing hydrogen such as gases from oil cracking, coke oven gas, producer gas, natural gas, etc.

The herein described process of my invention may be carried out in any conventional or desirable type of process for cracking hydrocarbon'.

oil. The attached drawing is a diagrammatic illustration in side elevation of one form o conventional cracking process wherein my invention is adaptable. In this drawing raw oil charging stock for the process may be passed from a source of supply through a line l, controlled by a valve 2, by means of a pump 3 and via line 4 to a heating coil 5 wherein said oil is subjected to thedesired conversion temperature and pressure. The highly heated oil from the coil 5 may then be passed via transfer' line 6, controlled by valve 7, to an enlarged reaction zone 8, wherein further conversion of the oil may take place, and wherein the liquid and vaporous products of reaction separate. The heavy, unvaporized residual products produced within the reaction zone 8 may be discharged from the systemthrough a line 9, controlled by a valve 10, while the lighter, vaporous products of reaction may be discharged from said zone through a line l1, controlled by a valve 12 into a suitable fractionating zone 13 wherein separation oi the lighter from the heavier components of said vapors occurs. The

separated and condensed, insuiciently converted Mid lauf

tion within said zone 13 :may be returned to the heating coil 5 for further conversion through a line 14 leading from said fractionating zone to the pump 3 which communicates with the line 4 leading to said heating coil. The lighter, sufficiently converted fractions produced in said fractionating zone maybe passed via line 15, controlled by valve 16, to a suitable condenser 17, from whence the liquefied product passes to a receiver 19, passage from said condenser to said receiver being controlled by a suitable valve 18. The incondensable gases produced in the system and collecting in the receiver 19 may be discharged from the latter through a suitably valved line 20, while the distillate collecting in said receiver may be withdrawn therefrom to suitable storage through a valved line 21.

Metallic hydrides for utilization in the process may be introduced, together with desired quantities of steam, either into the reaction zone 8 or into the fractionating zone 13,0r to both said reaction zone and said fractionating zone, whereby said hydrides may react with the hydrocarbons under treatment in either or both of said zones. For example, any suitable hydride, preferably while in iinely divided form may be introduced into the reaction zone 8`from a source of supply (not shown) through a line 22, controlled by valve 23, while steam may be introduced into said zone in regulated quantities from a convenient source (not shown) through a line 24, controlled by a valve 25. Likewise, any suitable hydride while preferably in finely divided form may be introduced into the fractionating zone 13 through a line 26, controlled by a Valve 27, together with regulated quantities of steam through a line 28, controlled by a valve 29.

Preferably the oil is heated to a cracking temperature, although my invention contemplates operating the process at lower temperatures also. Preferably the process is operated at atmospheric pressure or at super-atmospheric pressure, and may in some cases Aalso be operated at atmospheric or reduced or sub-atmospheric pressures. Generally I make use of super-atmospheric pressures ranging from pounds to 3000 pounds, more or less, and at temperatures of from approximately 400 degrees to 1400 degrees F.

As an example of the results obtained by the process, a 27 Baum gravity Mid-Continent topped crude when subjected to a cracking tem- 1,950,721y components of the vapors undergoing fractionaperature oi approximately 920 degrees F., and a pressure of approximately 1000 pounds using approximately 10% by weight of the hydride of sodium and 10% by weight of steam based on the oil charged, .shows an approximate yield of gasoline of sixty percent, in addition to approximately fifteen percent of pressure distillate'bottoms or gas oil which may be utilized as recycle stock. Coke and gas are also valuable products of the process. The sulphur content of the gasoline produced, which would normally be approximately 0.3 percent, may be reduced to approximately 0.1 percent.

The above example is purely illustrative and is not to be construed as a limitation of the broad scope of the invention.

I claim as my invention:

1. A process for hydrogenating hydrocarbon oil, comprising subjecting said oil to conversion conditions of temperature and pressure in a heating zone, passing the resultant products from said heating zone into a reaction zone wherein further conversion occurs, introducing the lighter products of reaction into a fractionating zone wherein the lighter, sufliciently converted fractions separate from the heavier, insuiiiciently converted fractions, the improvement which comprises introducing metallic hydrides and steam into the vapors undergoing treatment in said reaction zone and fractionating zone to eiect a liberation of nascent hydrogen and a saturation of said vapors.

2. A process for hydrogenating hydrocarbon oil, comprising subjecting said oil to cracking temperatures and pressures in a heating zone, introducing the highly heated products from said heating zone into an enlarged reaction zone wherein further conversion occurs and liquids and vapors separate, the liquid being withdrawn from the process, passing the vaporous products 'u of reaction into a fractionating zone for separation of its lighter from ents, the latter being returned to the heating zone, introducing metallic'hydrides and steam into the vapors undergoing treatment in said reaction and fractionating zones for generation of nascent hydrogen therein, and maintaining hydrogenation conditions of temperature and pressure in each of said reaction and fractionating zones.

GUSTAV EGLOFF.

its heavier constitu- 

